Compositions with Fast and Slow Release Components

ABSTRACT

The present invention relates to controlled release compositions that include: (a) a slow release component, comprising one or more performance additives in the form of a solid or semi-solid mass; and (b) a fast release component comprising (i) a matrix material and (ii) one or more additives that can be dissolved and/or dispersed into the matrix material as well as additive delivery systems and processes using such compositions, and which release one or more additives into a fluid.

FIELD OF THE INVENTION

The present invention relates to gel-containing systems that include:(a) a slow release component, comprising one or more performanceadditives in the form of a solid or semi-solid mass; and (b) a fastrelease component comprising (i) a matrix material and (ii) one or moreadditives that can be dissolved and/or dispersed into the matrixmaterial as well as additive delivery systems and processes using suchcompositions, and which release one or more additives into a fluid.

BACKGROUND OF THE INVENTION

Functional fluids degrade over time through use. The additives in thefunctional fluids deplete over the lifetime of the fluid in an engine orother mechanical device. The ability to supply additives to a fluid overits lifetime or use may help preserve and even improve the performanceof the functional fluid and the equipment in which it is used. Timerelease additives for engine oil are known. These additives aretypically incorporated into thermoplastic polymers which slowly dissolveinto the engine oil, see U.S. Pat. No. 4,075,098. Time release additiveshave also been incorporated into polymers which are oil-permeable atelevated engine temperatures, see U.S. Pat. No. 4,066,559.

Replenishment of additives in a functional fluid, by using a controlledrelease gel or other means to add additional additive to the functionalfluid, improves the performance of the functional fluid and the deviceusing the functional fluid. Use of controlled release gels, as describedin U.S. Pat. No. 6,843,916, has been shown to be an effective means toreplenish a lubricant with fresh additives over time. Such gels areformed by incorporating additive components which are compatible withthe functional fluid to which the additive is to be delivered into a gelmatrix. These gel matrixes often result from the interaction of a basiccomponent and an acidic component, forming the gel.

However, it would be beneficial to supply certain additives or groups ofadditives to a fluid at certain release rates while simultaneouslysupplying certain other additives or groups of additives to the samefluid, but at certain other release rates. It would also be beneficialto accomplish this independent, dual delivery while maintaining anintegrated additive package and/or system.

SUMMARY OF THE INVENTION

The present invention provides compositions, processes and additivedelivery systems that address the problems described above. The presentinvention allow for the controlled release of multiple additives to afunctional fluid and also allow for independent release rates for two ormore additives and/or groups of additives, thus allowing for morerefined and beneficial fluid conditioning, which in turn provideslengthened fluid life and/or improved fluid performance.

The present invention provides a composition comprising: (a) a slowrelease component that is made up of one or more performance additivesin the form of a solid or semi-solid mass, wherein the additivecomponents making up the mass are slowly released into a fluid; and (b)a fast release component that contains (i) a matrix material which issoluble in the fluid and (ii) one or more performance additives that canbe dissolved and/or dispersed into the matrix material. The performanceadditives within the matrix material may be quickly released into thefluid; and the weight ratio of components (a):(b) may be 1:100 to 100:1.

The invention further provides that components (a) and (b) may each bein the form of one or more distinct layers within the composition. Oneor more layers each of (a) and (b) can be combined to form a controlledrelease additive composition, wherein the layers of (a) and (b) may bearranged such that either component (a) and/or (b) may form one or moreexternal layers, internal layers, or interstitial layers of thecontrolled release additive composition.

The invention further provides a process of releasing, at controlledrates, one or more performance additives into a fluid, wherein eachadditive or group of additives is released at an independent rate;wherein at least one additive or group of additives is released slowlyover time into the fluid; and wherein at least one additive or group ofadditives is released quickly into the fluid; wherein process includesthe step of contacting the fluid with one or more of the compositionsdescribed above.

The invention further provides an additive delivery system that includesone or more of the controlled release compositions described above and ameans of contacting the composition with the fluid, resulting in thefast release of one more additives, and the slow release of one or moreadditives, into the fluid.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below byway of non-limiting illustration.

The present invention provides a performance additive controlled releasecomposition that contains: (a) a slow release component and (b) a fastrelease component. These two components may each be present in thecomposition in the form of one or more distinct layers. One or morelayers each of (a) and (b) are combined to form a controlled releaseadditive composition. The layers of (a) and (b) may be arranged suchthat either component (a) and/or (b) may form one or more externallayers, internal layers, or interstitial layers of the controlledrelease additive package.

In some embodiments, component (b), the fast release component, forms anexterior layer that completely encompasses component (a), the slowrelease component, and/or forms a barrier between component (a) and thefunctional fluid with which the combination is used. In otherembodiments, component (a) is completely encompassed by component (b),in the same manner as described above.

In some embodiments, components (a) and (b) are aligned and/orpositioned side by side or positioned such that one component partiallyencompasses the other. In such embodiments, some portions of both (a)and (b) are exposed to the functional fluid with which the combinationis used.

The ratio of components (a):(b) can be from 1:100 to 100:1, or 1:10 to10:1 or even 1:5 to 5:1. In some embodiments the ratio of components(a):(b) is from 100:1 or 90:10 or 80:20 to 40:60, or 50:50 or 60:40.

The release rate of an additive from the components described herein,into the functional fluid with which they are used, is the rate at whichone or more of additives that make up and/or are present in thecomponent of the performance additive controlled release composition isreleased from the component to the functional fluid. The release rate isdetermined primarily by the formulation of the component and/or overallcomposition. The release rate is also dependent on the mode of additionof the performance additive controlled release composition, the physicalorientation and arrangement of the components that make up thecomposition, the location of the composition within the system thatutilizes the functional fluid, the flow rate of the functional fluid inthe system and particularly in the part of the system where thecomposition is located, and the form of the components of the additivecomposition (e.g., stiffness, consistency, homogeneity and the like) andthe like.

The Slow Release Component

The slow release component of the present invention may comprise one ormore performance additives and be in the form of a solid or a semi-solidmass, such as a gel. The additive components making up the slow releasecomponent are slowly released into the fluid with which it is used.

By slow release, it is meant that one or more of the additives in theslow release component are released into the functional fluid with whichit is used at a rate slower than the release rate of the fast releasecomponent. In one embodiment, slow release means that no more than 80 wt% of component (a) is released into the functional fluid with which itis used over the first 50% or more of the fluid's service life. In otherembodiments no more than 70, 80, 90, or even 95 wt % of component (a) isreleased into the functional fluid over the first 50, 60, or 70% of thefluid's service life. In other embodiments the amount of the fastrelease component may be measured relative to the amount of slow releasecomponent released or instead to the total amount of release of theadditives in both components. In some of these embodiments, at the pointwhere up to 60 wt % of the additives to be released from the overallcomposition have been released, no more than 40 wt % of the additives tobe released from the slow release component will have been released. Insome of these embodiments, at the point where up to 50 wt % of theadditives to be released from the overall composition have beenreleased, no more than 31 wt % of the additives to be released from theslow release component will have been released.

A fluid's service life is the period during which a fluid is utilized inthe application and/or equipment for which it has been designed. Servicelife may be a fluid's useful life, that is the period during which afluid can effectively perform its designed function. Service life may bea preset period selected by a fluid's manufacture and/or retailer or themanufacture and/or retailer of the equipment in which the fluid isutilized. Service life may be determined by monitoring the fluidinvolved, and using data collected from the fluid to determine when itsservice life will end or has ended. As an example, an engine'slubricating oil's service life starts when the oil is added to theengine and ends when the oil is changed. Service life may be measured bytime, such as the amount of time since the fluid has been added to apiece of equipment and/or the amount of time the equipment has beenoperated since the fluid was added. Service life may be measured byunits of distance, as in the case of a vehicle engine where the engineoil may be changed after so many miles traveled. Service life may bemeasure by a number of operations, such as a piece of manufacturingequipment, where the fluid life is measured by the number if cyclescompleted and/or number of units produced.

Component (a), the slow release component, can be a performance additivegel. Gels are materials that comprise mixtures of two or more substancesand which exist in a semi-solid state more like a solid than a liquid. Agel exists in a semi-solid state more like a solid than a liquid, seeParker, Dictionary of Scientific and Technical Terms, Fifth Edition,McGraw Hill, © 1994. See, also, Larson, “The Structure and rheology ofComplex Fluids”, Chapter 5, Oxford University Press, New York, N.Y., ©1999, each which is incorporated herein by reference. The rheologicalproperties of a gel can be measured by small amplitude oscillatory sheartesting. This technique measures the structural character of the gel andproduces a term called the storage modulus which represents the storageof elastic energy and the loss modulus which represents the viscousdissipation of that energy. The ratio of the loss modulus/storagemodulus, which is called the loss tangent, or “tan delta”, is ≧1 formaterials that are liquid-like and ≦1 for materials that are solid-like.The gels herein can have tan delta values of about ≦1 or ≦0.95, or about≦0.75, or in other embodiments of about ≦0.5 or ≦0.3.

Gel compositions can also be evaluated by using a cone penetrometer,according to ASTM D 217. The cone penetrometer (cone pen) value obtainedis one measurement of the stiffness and/or firmness of a gel. In oneembodiment, the additive gel compositions of the present invention havea cone pen value of 300 or less, 200 or less, or from 30 to 200, or from40 to 165.

Gel compositions suitable for use in the present invention are typicallymade by blending of a mixture of additives selected to simultaneouslyprovide the desired performance and to form a gel upon mixing or mixingwith subsequent thermal curing. In some embodiments, the gel compositionis formed by combining at least two components selected from the groupconsisting of: detergents, dispersants, acids, bases, over baseddetergent, and succinated polyolefins. The components are selected, andcombined in specific ratios, so that when combined, they form a gel.

The gel's formulation may be composed of: (i) a basic componentcomprising an overbased detergent, an ashless dispersant, or mixturesthereof; (ii) an acidic component comprising a maleic anhydridestyrene-copolymer or an ester thereof, an ashless dispersant,polyolefin, succinated polyolefin or mixtures thereof; (iii) an additivecomponent which is substantially insoluble in, has low solubility in, oris otherwise incompatible with a functional fluid, as described aboveand referred to as an “incompatible additive” herein; and (d) optionallyat least one additive comprising one or more viscosity modifiers,friction modifiers, detergents, cloud point depressants, pour pointdepressants, demulsifiers, flow improvers, antistatic agents,dispersants, antioxidants, antifoams, corrosion/rust inhibitors, extremepressure/antiwear agents, seal swell agents, lubricity aids, antimistingagents, or combinations thereof.

The basic component can be an overbased detergent, an ashless dispersantwith a total base number (TBN) greater than 13, or mixtures thereof.

Dispersants suitable for use in the basic component include ashlessdispersants such as a polyisobutylene succinimide and the like so longas the dispersant has a total base number (TBN) greater than 13.Polyisobutylene succinimide ashless dispersants arecommercially-available products which are typically made by reactingtogether polyisobutylene having a number average molecular weight (“Mn”)of about 300 to 10,000 with maleic anhydride to form polyisobutylenesuccinic anhydride (“PIBSA”) and then reacting the product so obtainedwith a polyamine typically ethylene polyamines containing 2 to 10nitrogen atoms per molecule.

Detergents suitable for use in the basic component include overbasedsulfonates, phenates, salicylates, carboxylates, overbased calciumsulfonate detergents which are commercially-available, overbaseddetergents containing metals such as Mg, Ba, Sr, Na, Ca and K andmixtures thereof and the like.

The basic component may further comprise copolymers such asethylene-propylene diene monomer (EPDM) copolymer. Suitableethylene-propylene diene monomer (EPDM) copolymers include those with anumber average molecular weight between 1×10² and 1×10⁹. In oneembodiment the basic component comprises a copolymer, an overbaseddetergent, or a combination thereof. In one embodiment the copolymercomprises an ethylene-propylene diene monomer (EPDM) copolymer. Inanother embodiment the overbased detergent comprises an overbasedcalcium alkylbenzenesulfonate detergent. In yet another embodiment theEPDM copolymer and the overbased calcium alkylbenzenesulfonate detergentare used in combination with one another.

The basic component may be present in ranges such that the weight ratioof the basic component to the acidic component is, in one embodiment,0.01 to 0.99:1, and in another embodiment 0.05 to 0.2:1. Thiscorresponds to a range of about 1% by weight to about 100% by weight inone embodiment for the combined basic and acidic components in the gel,and a range of about 1% by weight to about 50% by weight in anotherembodiment. As to the basic component alone, the gel may be, in oneembodiment, about 0.1% by weight to about 80% by weight basic componentand in another embodiment, about 0.5% by weight to about 70% by weightbasic component. In still other embodiments, the basic component ispresent in the gel from 0.5% by weight to 60% by weight, from 30 to 60%by weight, from 40 to 60% by weight, from 50 to 60% by weight, or from55 to 58% by weight.

The acidic component of the gel may comprise a functionalized polymerwith an acidic group, an ashless dispersant, a polyolefin, a succinatedpolyolefin or mixtures thereof.

Functionalized polymers useful in the present invention include olefincopolymers and acrylate or methacrylate copolymers. Functionalizedolefin copolymers can be, for instance, interpolymers of ethylene andpropylene which are grafted with an active monomer such as maleicanhydride and then derivatized with an alcohol or an amine. Other suchcopolymers are copolymers of ethylene and propylene which are reacted orgrafted with nitrogen compounds. Derivatives of polyacrylate esters arewell known as dispersant viscosity index modifiers additives. Dispersantacrylate or polymethacrylate viscosity modifiers such as Acryloid™ 985or Viscoplex™ 6-054, from RohMax, are particularly useful. Solid,oil-soluble polymers such as polyisobutylene, methacrylate,polyalkylstyrene, ethylene/propylene andethylene/propylene/1,4-hexadiene polymers, can also be used as viscosityindex improvers.

In one embodiment, the acidic component of the present inventioncomprises maleic anhydride styrene copolymer (MSC) and may furthercomprises an ashless dispersant.

The maleic anhydride styrene copolymer may be partially esterified withan alcohol where the equivalent ratio of alcohol to acid groups is inone embodiment from about 0.1 to about 0.99 and in another embodimentfrom 0.45 to 0.95. Appropriate alcohols for use in preparing thecopolymer include alcohols containing 6 to 32 carbon atoms, and inanother embodiment, alcohols containing 8 to 18 carbon atoms. Suitablemaleic anhydride styrene copolymers comprise those with a total acidnumber (TAN), in one embodiment, greater than 1, and in anotherembodiment greater than 3 where TAN is in the units of milligrams of KOHper gram of material.

The ashless dispersants suitable for use in the acidic component are thesame as the dispersants described above in regards to the basiccomponent except that suitable ashless dispersants for use in the acidiccomponent have a measurable total acid number (TAN). In some embodimentssuitable dispersants have a TAN greater than 15. In one embodiment, theacidic component comprises a polyisobutylene succinimide dispersant.

The acidic component may be present in ranges such that the weight ratioof the basic component to the acidic component is typically 0.01 to0.99, and more typically 0.05 to 0.2. This corresponds to a range ofabout 1% by weight to about 100% by weight in one embodiment for thecombined basic and acidic components in the gel, and a range of about 1%by weight to about 50% by weight in another embodiment. As to the acidiccomponent alone, the gel may be, in one embodiment, about 0.5% by weightto about 99% by weight acidic component and in another embodiment, about0.5% by weight to about 98% by weight acidic component. In otherembodiment the acidic component may be present in the gel from 0.1% to40% by weight, from 0.1% to 20% by weight, from 0.1% to 10% by weight,or from 5 to 10% by weight.

The gel compositions of the present invention may contain at least oneadditional desired additive for controlled release into the functionalfluid. These optional gel component additives include viscositymodifier(s), friction modifier(s), detergent(s), cloud pointdepressant(s), pour point depressant(s), demulsifier(s), flowimprover(s), anti static agent(s), dispersant(s), antioxidant(s),antifoam(s), corrosion/rust inhibitor(s), extreme pressure/antiwearagent(s), seal swell agent(s), lubricity aid(s), antimisting agent(s),and mixtures thereof with the proviso that these additional additivesare not the same as the additives present in any of the other componentsin the gel composition, though they may be the same type of additive,and they may be the same as additives that are already present in thefunctional fluid with which the gel composition is used. The presence ofone or more of these optional additives results in a controlled releasegel that over time releases the desired additive(s) into a functionalfluid when the gel is contacted with the functional fluid. The desiredadditive component is further determined by the functional fluidformulation, performance characteristics, function and the like and whatadditive is desired to be added for depleted additives and/or added newdepending on the desired functions.

The optional additive component comprising one or more desired additivesfor controlled release, when present, is present in ranges such that theweight ratio of the optional additive component to the combined total ofgel components is in one embodiment 0.001 to 0.99, and in anotherembodiment 0.01 to 0.5. This corresponds to a range of about 0% byweight to about 99% by weight in one embodiment of the optional additivecomponent in the gel and a range of about 1% by weight to about 50% byweight in another embodiment. In other embodiments the optional additivecomponent is present in the gel from 0 to 40% by weight, from 0 to 30%by weight, from 0 to 25% by weight, from 0 to 20% by weight, from 0 to20% by weight, from 15 to 30% by weight, and from 15 to 25% by weight.

Suitable antioxidants include, but are not limited to aromatic amines,alkyl-substituted phenols, sterically hindered phenols (such as2,6-di-tert-butylphenol), and hindered ester-substituted phenols.

Suitable extreme pressure/anti-wear agents include sulfur and/orchlorosulphur EP agents, chlorinated hydrocarbon EP agents, phosphorusEP agents, or mixtures thereof.

Suitable antifoams include organic silicones such as polydimethylsiloxane, polyethylsiloxane, polydiethylsiloxane, polyacrylates andpolymethacrylates, trimethyl-triflouro-propylmethyl siloxane and thelike.

Suitable viscosity modifiers include vinyl pyridine,N-vinyl-2-pyrrolidone and N,N′-dimethylaminoethyl methacrylate as wellas polyacrylates obtained from the polymerization of one or more alkylacrylates.

Suitable friction modifiers include organo-molybdenum compounds,including molybdenum dithiocarbamate, and fatty acid based materials,including those based on oleic acid (such as glycerol mono oleate) andstearic acid and hydroxy acids such as tartaric acid, malic acid andcitric acid. Examples of this last type include hydroxy acid derivedesters and imides having a hydrocarbon group containing from 8 to 20carbon atoms.

Suitable anti-misting agents include very high (>100,000 Mn) polyolefinssuch as 1.5 Mn polyisobutylene (for example the material of the tradesname Vistanex®), or polymers of 2-(N-acrylamido)-2-methyl propanesulfonic acid (also known as AMPS®), or derivatives thereof, and thelike.

Suitable corrosion inhibitors include alkylated succinic acids andanhydrides derivatives thereof, organo phosphonates and the like. Therust inhibitors may be used alone or in combination.

Suitable metal deactivators include derivatives of benzotriazoles (suchas tolyltriazole and the like). Suitable demulsifiers includepolyethylene oxide and polypropylene oxide copolymers and the like.Suitable lubricity aids include glycerol monooleate, sorbitan monooleateand the like. Suitable flow improvers include ethylene vinyl acetatecopolymers and the like. Suitable cloud point depressants includealkylphenols, and specifically waxy coupled alkylphenols, andderivatives thereof, ethylene vinyl acetate copolymers and the like.Suitable pour point depressants include alkylphenols and derivativesthereof, ethylene vinyl acetate copolymers and the like. Suitable sealswell agents include organo sulfur compounds such as thiophenederivatives, 3-(decyloxy)tetrahydro-1,1-dioxide (i.e.3-decyloxysulfolane) and the like.

In some embodiments the optional additive component may comprisedispersants and detergents such as those above. In addition, theoptional additive component may also comprise additional types ofdispersants. These additional types of dispersants include Mannichdispersants, carboxylic dispersants, amine dispersants, and polymericdispersants.

The Mannich dispersant are the reaction products of alkyl phenols inwhich the alkyl group contains at least about 30 carbon atoms withaldehydes (especially formaldehyde) and amines (especially polyalkylenepolyamines).

Another class of dispersants is carboxylic dispersants. Examples ofthese “carboxylic dispersants” are described in Patent U.S. Pat. Nos.3,219,666 and 3,172,892.

Amine dispersants are reaction products of relatively high molecularweight aliphatic halides and amines, preferably polyalkylene polyamines.Examples thereof are described, in U.S. Pat. No. 3,565,804.

Polymeric dispersants are interpolymers of oil-solubilizing monomerssuch as decyl methacrylate, vinyl decyl ether and high molecular weightolefins with monomers containing polar substituents, e.g., amino alkylacrylates or acylamides and poly-(oxyethylene)-substituted acrylates.Examples of polymer dispersants thereof are disclosed in the followingU.S. Pat. No. 3,329,658, and 3,702,300.

Dispersants can also be post-treated by reaction with any of a varietyof agents. Among these are urea, thiourea, dimercaptothiadiazoles,carbon disulfide, aldehydes, ketones, carboxylic acids,hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boroncompounds, and phosphorus compounds.

Optionally, other components can be added to the additive gel whichincludes base stock oils, inert carriers, dyes, bacteriostatic agents,solid particulate additives, and the like so long as the free standingadditive gel is maintained.

In some embodiments the gels of the present invention are free fromthermoplastic polymers. In such embodiments the gels of the presentinvention may be substantially free of thermoplastic polymers orcompletely free of thermoplastic polymers.

In one embodiment, the gel composition used as the slow releasecomponent of the present invention is prepared by mixing a detergent,(which may be a sulfonate, phenate, salicylate carboxylate or mixturesthereof) with a dispersant, (which may be a N-substituted long chainalkenyl succinimide, polyisobutylene succinimide, high molecular weightester, Mannich base, amine dispersant, polymeric dispersant or mixturesthereof) and/or an acid, (which may be a polymer containing acidicgroups in the backbone, a polyacidic compound, or mixtures thereof).

Component (a), the slow release component, can be a solid. The solid canbe a material that (i) has a melting point from 40 to 250° C., 50 to150° C. or even 60 to 120° . The solid can be a material that (ii) is atleast partially soluble in the fluid with which the overall compositionis used. The solid can be a material that (iii) is formed by mixing ofone or more additives, such additives may include viscosity modifiers,friction modifiers, ashless detergents, cloud point depressants, pourpoint depressants, demulsifiers, flow improvers, anti static agents,ashless dispersants, ashless antioxidants, antifoams, corrosion/rustinhibitors, extreme pressure/antiwear agents, wear reducing agents, sealswell agents, lubricity aids, antimisting agents and mixtures thereof.The solid may possess one or more of the characteristics (i), (ii) and(iii) described above.

When the slow release component is contacted with a functional fluid,the additives that make up the slow release component, including theadditives described above as well as the additional additives providedfor below, are released into the fluid at a slow rate, as defined above.

Component (a), the slow release component, may be more than 70 wt %dispersant and detergent and/or may be more than 45 wt % detergent.

Both component (a), the slow release component described above, andcomponent (b), the fast release component described below, may furthercontain one or more additional performance additives. Suitable additivesinclude viscosity modifiers, friction modifiers, ashless detergents,cloud point depressants, pour point depressants, demulsifiers, flowimprovers, antistatic agents, ashless dispersants, ashless antioxidants,antifoams, corrosion/rust inhibitors, extreme pressure/antiwear agents,wear reducing agents, seal swell agents, lubricity aids, antimistingagents and mixtures thereof. These additional additives may notparticipate in forming the gel and/or matrix materials described herein,but may instead be present in the compositions without any suchinteraction.

The Fast Release Component

The fast release component of the present invention may comprise (i) amatrix material which can be soluble in the functional fluid with whichit is to be used and (ii) one or more additives that can be dissolvedand/or dispersed into the matrix material. The additives present in thefast release component are quickly released into the fluid with which itis used.

By fast release, it is meant that one or more of the additives presentin the fast release component are released into the functional fluidwith which it is used at a rate faster than the release rate of the slowrelease component. In one embodiment, fast release means that at least80 wt % of component (b) is released into the functional fluid withwhich it is used over the first 25% or less of the fluid's service life.In other embodiments at least 80, 90, 95 or even 100 wt % of component(a) is released into the functional fluid over the first 25, 20, or 10%of the fluid's service life. The service life of a fluid is definedabove.

The matrix material can be a solid, as described above, including waxymaterials with melting points just above, or just below, or about at theoperating temperature of the functional fluid with which it is used.With regards to the matrix material of the fast release component, theterm soluble means that the matrix materials can fully dissolve into thefunctional fluid in which the overall composition is used, however suchdissolution may not occur immediately, but rather over an extendedperiod of time, even longer than the time during which the additivesdescribed above are releases into the fluid. In some embodiments thematrix material is a solid at ambient conditions but melts to a liquidat the conditions present in the functional fluid during the fluids use,resulting in the matrix material melting. In such embodiments the meltedmatrix material is fully soluble in the functional fluid and would mixinto it immediately.

The additives which may be dispersed into the matrix material includeglycerol esters, borated glycerol esters, fatty phosphites, fatty acidamines, fatty epoxides, borated fatty epoxides, alkoxylated fattyamines, borated alkoxylated fatty amines, metal salts of fatty acids,sulfurized olefins, fatty imidazolines, condensation products ofcarboxylic acids and polyalkylene-polyamines, amine salts ofalkylphosphoric acids, molybdenum-containing friction modifiers,friction modifiers derived from hydroxy acids such as tartaric acid,malic acid and citric acid, or combinations thereof, so long as theadditives are different from the matrix material. When the fast releasecomponent is contacted with a functional fluid, these additives arereleased from the matrix material into the fluid at a fast rate, asdefined above.

Processes and Additive Delivery Systems

The present invention provides a process by which two or more additivesor groups of additives are effectively delivered to a functional fluidat two or more independent release rates. The method of the presentinvention comprises the use of an additive composition which containsone or more each of the slow release and fast release componentsdescribed above, and the contacting of the functional fluid and theadditive composition, resulting in the delivery of the additives to thefunctional fluid at the different rates

The present invention may be utilized in any fluid conditioning deviceor system including internal combustion engines which include mobile andstationary applications; hydraulic systems; automatic transmissions;gear boxes which include manual transmissions and differentials;metalworking fluids; pumps; suspension systems; other lubricatedmechanical systems; and the like. The fluid conditioning devices thatcan use the gel include, internal combustion engines, stationaryengines, generators, diesel and/or gasoline engines, on highway and/oroff highway engines, two-cycle engines, aviation engines, pistonengines, marine engines, railroad engines, biodegradable fuel enginesand the like; lubricated mechanical systems such as gear boxes,automatic transmissions, differentials, hydraulic systems and the like.In some embodiments, the present invention may be used with aqueous ororganic functional fluids. In other embodiments the present invention isused to deliver additives to organic functional fluids only.

The functional fluids useful to being further additized through themethods and gel compositions of the present invention include gear oil,transmission oil, hydraulic fluid, engine oil, two cycle oil,metalworking fluid and the like. In one embodiment the preferredfunctional fluid is an engine oil. In another embodiment the preferredfunctional fluid is gear oil. In another embodiment the preferredfunctional fluid is transmission fluid. In another embodiment thepreferred functional fluid is a hydraulic fluid.

The additive compositions dissolve into and/or supply the additivescontained within the slow and fast release components to a functionalfluid through the contacting of the additive compositions with thefunctional fluid. The additive composition may be positioned anywhere ina system or piece of equipment where the additive composition will be incontact with the functional fluid. In one embodiment, the additivecomposition is positioned anywhere within a piece of equipment throughwhich a functional fluid circulates and where the functional fluid maycontact the additive composition.

In one embodiment the functional fluid is an engine oil and the additivecomposition is positioned in the engine oil system which can include anyof the following: the lubricating system, filter, drain pan, oil bypassloop, canister, housing, reservoir, pockets of a filter, canister in afilter, mesh in a filter, canister in a bypass system, mesh in a bypasssystem, oil lines and the like. In one embodiment the functional fluidis a gear oil and the additive composition is located in the gear systemwhich can include any of the following: drain pan, sump, filters, a fullflow or bypass oil line, lines, loop and/or filter, canisters, mesh,other spaces within the device in which a additive composition might becontained and the like. In one embodiment the functional fluid istransmission fluid and the additive composition is located in thetransmission system which can include any of the following: the spacesuch as a hole within a transmission magnet, the oil pan, oil lines,lines, canisters, mesh and the like. In one embodiment the additivecomposition is located in the engine oil line, which can include any ofthe following: a full flow filter, a by-pass filter, the oil pan, andthe like. In one embodiment, the functional fluid is a hydraulic fluidand the additive composition is located in the hydraulic cylinder, sump,filter, oil lines, pan, full flow or by pass oil loop, line and/orfilter, canister, mesh, other spaces in the system and the like.

One or more locations in a line, loop and/or the functional fluid systemcan contain the additive composition. Further, if more than one additivecomposition is used each, each additive composition can be an identical,similar and/or a different additive composition than the other additivecompositions used.

In some embodiments the invention provides a container to hold theadditive composition, such as a housing, a canister or a structural meshanywhere in the functional fluid system, for example, a canister withina bypass loop of a stationary gas engine for power generation. Thenecessary design feature for the container is that at least a portion ofthe additive composition is in contact with the functional fluid. Inother embodiments, the additive composition is used without such acontainer. In still other embodiments the additive composition istethered, anchored, or otherwise fixed to a position within the fluidsystem in which the functional fluid is used and so in this way is notcontained within a additive composition cup or similar container.

In some embodiments, the additive composition itself is considered to bethe delivery device that enables the delivery of the substantiallyinsoluble or low solubility additive to the functional fluid. In otherembodiments the container in which the additive composition is locatedis considered to be the delivery device. In still other embodiments, thedelivery device is considered to be a device, such as a filter, in whichthe additive composition, which may or may not be located within acontainer, is located. The primary feature of the delivery device,across all of the embodiments described, is its ability to allow for,and in some embodiments to facilitate and/or control, the contacting ofthe functional fluid and the additive composition.

The additive composition needs to be in contact with the functionalfluid. In one embodiment the additive composition is in contact with thefunctional fluid in the range of about 100% to about 1% of thefunctional fluid in the system, in that 1 to 100% of the functionalfluid comes into physical contact with the additive composition duringthe fluid's use. In other embodiments the additives is exposed to 1 to100% of the flow of the functional fluid in the system. Generallyspeaking, as the flow rate of the functional fluid as it contacts theadditive composition decreases there is less dissolution of the additivecomposition into the fluid, and as the flow rate increases there isgreater dissolution of the additive composition.

In one embodiment, the additive composition is positioned in thefunctional fluid system so that the additive composition and/or spentadditive composition can easily be removed from the functional fluidsystem, and then replaced with a new and/or recycled additivecomposition. In some embodiments the additive composition is containedin a cartridge or similar device, facilitating such removal andreplacement.

The additive composition of the present invention may comprise a freestanding gel or a non-free standing gel. A free standing gel can be usedwithout being contained inside a form that holds the gel's shape anddimensions. A non-free standing gel is prepared in a container fromwhich the gel cannot be removed intact. The gel and its forming deviceboth become part of any functional fluid conditioning device the gel isused in. A free standing gel, once formed, can be removed intact fromits forming device and can be placed or built into a functional fluidconditioning device without the need of integrating the forming deviceinto the functional fluid conditioning device. In some embodiments thefree standing gel can be placed into a conditioning device, or otherwiseused, without any container at all. This provides the opportunity todesign the gel forming or curing container separately from the fluidconditioning device, reducing manufacturing costs of the gel and theconditioning devices. In some embodiments, considered alone or incombination with one or more of the embodiments provided both above andbelow, the free standing gels of the present invention are brought intocontact with a functional fluid without the presence of a container orholding device surrounding or otherwise containing the gel, or if anytype of container or holder is used with the gel, no side wall orsimilar structure is present.

The additive delivery systems of the present invention utilize theprocesses and compositions described above and may be integrated intothe functional fluid utilizing equipment described above. The additivedelivery systems of the present invention may be integrated into adevice's functional fluid system, for example, the additive deliverysystem may be an insert and/or form that is placed in the lubricantsystem or fuel system of an internal combustion engine. In someembodiments, the additive composition is contained within a fluid filterand one or more of the additives that make up the composition arereleases into the fluid as it passes through the fluid filter and with adevice that utilizes said fluid, with additives contained in the slowrelease component being released slowly and additives in the fastrelease component being released more quickly.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude: hydrocarbon substituents, that is, aliphatic (e.g., alkyl oralkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, andaromatic-, aliphatic-, and alicyclic-substituted aromatic substituents,as well as cyclic substituents wherein the ring is completed throughanother portion of the molecule (e.g., two substituents together form aring); substituted hydrocarbon substituents, that is, substituentscontaining non-hydrocarbon groups which, in the context of thisinvention, do not alter the predominantly hydrocarbon nature of thesubstituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy,mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); heterosubstituents, that is, substituents which, while having a predominantlyhydrocarbon character, in the context of this invention, contain otherthan carbon in a ring or chain otherwise composed of carbon atoms.Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituentsas pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,preferably no more than one, non-hydrocarbon substituent will be presentfor every ten carbon atoms in the hydrocarbyl group; typically, therewill be no non-hydrocarbon substituents in the hydrocarbyl group.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. For instance,metal ions (of, e.g., a detergent) can migrate to other acidic oranionic sites of other molecules. The products formed thereby, includingthe products formed upon employing the composition of the presentinvention in its intended use, may not be susceptible of easydescription. Nevertheless, all such modifications and reaction productsare included within the scope of the present invention; the presentinvention encompasses the composition prepared by admixing thecomponents described above.

SPECIFIC EMBODIMENTS

The invention will be further illustrated by the following examples,which sets forth particularly advantageous embodiments. While theexamples are provided to illustrate the present invention, they are notintended to limit it.

Example 1

The Additive Composition

A composition designed to release multiple friction modifiers, acorrosion inhibitor, and an antioxidant at a fast release rate whilesimultaneously releasing friction modifiers, dispersants, and adetergent at a slow release rate, to an engine oil during the operationof an internal combustion engine is described below.

A fast release component is prepared by mixing a boron-containingcorrosion inhibitor (2.9 grams), an ashless amide-containing frictionmodifier (12.9 grams), a molybdenum-containing friction modifier (2.3grams), an ashless fatty acid derived friction modifier (5.7 grams), anda hindered phenol antioxidant (4.6 grams). The additives are mixed at100° C. for 12 hours.

A slow release component is prepared by mixing an ashless fatty acidderived friction modifier (4.8 grams), an overbased calcium sulfonatedetergent (25.4 grams, which is 42% wt oil), a polyisobutylenesuccinimide dispersant derived from 2000 number average molecular weightpolyisobutylene (8.3 grams, which is 47% wt oil), amolybdenum-containing friction modifier (1.9 grams), and apolyisobutylene succinic anhydride dispersant derived from 2000 numberaverage molecular weight polyisobutylene (6.6 grams). All of thecomponents, except for the detergent, are mixed at 55° C. The mixtureand the detergent are then combined, with stirring, into a cylindricalcup having a diameter of 6.35 cm (2.5 inch) and a height of 3.8 cm (1.5inches). The cup, containing the resulting mixture, is placed in an ovenat 100° C. for 12 hours. During this hold, the mixture forms a gel.

Once the slow release component has formed a gel, the fast releasecomponent, still at 100° C., is added to the cylinder, pouring it on topof the slow release component already present in the cylinder. Thematerial is allowed to cool, forming a solid layer in the cylinder,completely covering the slow release component below it. A lid is placedon the cylinder, where the lid has multiple 2 mm holes. The steps arerepeated and the resulting containers are used in Examples 2 and 3.

Example 2

A filled container of Example 1 is placed at the crown end (opposite ofthe engine interfacing end) of an oil filter, the filter being of thesame size and fittings as a Fram™ PH4967 oil filter, as described inU.S. Pat. No. 6,843,916. The filter is installed on a 2.2 L, 4-cylinder1997 Toyota Camry™ The case is then driven under normal stop-and-go andhighway conditions for 7163 km (4451 miles), with oil samples taken atregular intervals. The elemental composition (amount of Mo and Capresent in the oil) is measured by inductively couple plasma and thenused to calculate the amount of Ca and Mo released from the compositionin the container to the oil. The coefficient of friction (COF) of theoil is also measured. The results are shown in the table below.

TABLE 1 % Ca % Mo % Mo KMs Released in Oil Released COF 0  0% 0.0001% 1% 0.140 2  1% 0.0042% 36% 243  6% 0.0048% 42% 396  7% 0.0048% 42%0.127 644 15% 0.0050% 46% 0.120 1127 31% 0.0058% 53% 0.122 1487 40%0.0068% 60% 0.129 1984 52% 0.0099% 64% 0.129 2723 59% 0.0095% 67% 0.1293520 63% 0.0079% 70% 0.129 4477 71% 0.0080% 72% 0.134 5398 78% 0.0079%73% 0.131 7163 0.0080% 77% 0.136 END¹ 82% 92% ¹The End of Test Samplewas taken from the oil after it was drained from the engine

The results show that the Mo-containing additive, the majority of whichwas present in the fast release component, is released into the oil morequickly than the Ca-containing additive, which is only present in theslow release component. The data shows that more than 50% of theMo-containing additive had been released into the oil by the 1127 kmmark (after roughly 16% of the test period), while less than a third ofthe Ca-containing additive had been released. The results show that theMo content in the engine oil increases sharply at the beginning of thetest, indicating a fast release of the additive from the fast releasecomponent and then a slow increase over time, as the Mo-containingadditive is released from the slow release component. The results alsoshow that the COF decreased significantly at the start of the test andthen stabilized during before beginning to increase at the end,indicating the friction modifiers in the fast release component werebeing released into the oil.

Example 3

The test procedure of Example 2 is repeated except that the vehicle wasdriven under similar conditions for 2863 km (1779 miles). The resultsare shown in the table below.

TABLE 2 % Ca % Mo % Mo KMs Released in Oil Released COF 0  0% 0.0001% 0% 0.132 161 12% 0.0065% 55% 0.122 435 26% 0.0067% 58% 0.129 901 34%0.0077% 66% 0.133 1690 41% 0.0087% 74% 0.132 2504 57% 0.0094% 81% 0.1322863 63% 0.0096% 84% 0.135

The results here again show that the Mo-containing additive, themajority of which was present in the fast release component, is releasedinto the oil more quickly than the Ca-containing additive, which is onlypresent in the slow release component. The data shows that about 75% ofthe Mo-containing additive had been released into the oil by the 1690 kmmark (after roughly 60% of the test period), while about 40% of theCa-containing additive had been released. The results show that the Mocontent in the engine oil increases sharply at the beginning of thetest, indicating a fast release of the additive from the fast releasecomponent and then a slow increase over time, as the Mo-containingadditive is released from the slow release component. The results alsoshow that the COF decreased significantly at the start of the test andthen stabilized during before beginning to increase at the end,indicating the friction modifiers in the fast release component werebeing released into the oil.

Comparative Example 4

The test procedure of Example 2 is repeated except that the oil filterused does not have a container from Example 1 present. Instead 35 gramsof the same Mo-containing friction modifier as that used in thecomposition of Example 1 is added as a top-treat to the engine oil inthe crankcase. The vehicle was then driven under similar conditions for5757 km (3577 miles). The results are shown in the table below.

TABLE 3 % Mo KMs in Oil COF 0 0.0106% 0.121 109 0.0103% 0.120 4020.0100% 0.124 1164 0.0106% 0.126 1687 0.0103% 0.126 3158 0.0102% 0.1334960 0.0100% 0.134 5757 0.0108%

The results of the comparative example show that when the Mo-containingfriction modifier is added as a top treat material, the Mo content inthe oil stays constant over the duration of the test. This show that theincrease in Mo content seen in Examples 2 and 3 is from the controlledrelease of the Mo-containing friction modifier from the additivecomposition to the engine oil. In addition, the results show that theCOF of the oil starts at a low value and then slowly climbs over thecourse of the test. This is in contrast to Examples 2 and 3, where thecontrolled release of the additive results in a reduction in the COF inthe early part of the test, and then maintains the COF at a low leveluntil the very end of the test. It is also important to note that 35grams of the Mo-containing friction modifier was added to engine inorder to see this impact on COF, while only 4.2 grams is present in theadditive composition used to achieve comparable and/or improved results.

Although only a few embodiments of the present invention have beendescribed above, it should be appreciated that many modifications can bemade without departing from the spirit and scope of the invention. Allsuch modifications are intended to be included within the scope of thepresent invention, which is to be limited only by the following claims.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” Unless otherwise indicates all percent values and ppm valuesherein are weight percent values and/or calculated on a weight basis.Unless otherwise indicated, each chemical or composition referred toherein should be interpreted as being a commercial grade material whichmay contain the isomers, by-products, derivatives, and other suchmaterials which are normally understood to be present in the commercialgrade. However, the amount of each chemical component is presentedexclusive of any solvent or diluent, which may be customarily present inthe commercial material, unless otherwise indicated. It is to beunderstood that the upper and lower amount, range, and ratio limits setforth herein may be independently combined. Similarly, the ranges andamounts for each element of the invention can be used together withranges or amounts for any of the other elements. As used herein, theexpression “consisting essentially of” permits the inclusion ofsubstances that do not materially affect the basic and novelcharacteristics of the composition under consideration.

In addition, all the embodiments described above have been contemplatedas to their use, both alone and in combination, with all of the otherembodiments described above, and these combinations are considered to bepart of the present invention. The specific embodiments of amines andalcohols described above have been contemplated in combination with thespecific embodiments of the carboxylic acids useful in the presentinvention.

1. A composition comprising: (a) a slow release component comprising oneor more performance additives in the form of a solid or semi-solid mass,wherein the additive components making up the mass are slowly releasedinto a fluid; and (b) a fast release component comprising: i. a matrixmaterial which is soluble in the fluid; ii. one or more additives thatcan be dissolved and/or dispersed into the matrix material; wherein theadditives within the matrix material are quickly released into thefluid; and wherein the weight ratio of components (a):(b) is 1:100 to100:1.
 2. The composition of claim 1 wherein components (a) and (b) areeach in the form of one or more distinct layers, wherein the one or morelayers each of (a) and (b) are combined to form a controlled releaseadditive package, wherein the layers of (a) and (b) may be arranged suchthat either component (a) and/or (b) may form one or more externallayers, internal layers, or interstitial layers of the controlledrelease additive package.
 3. The composition of claim 1 wherein (a), theslow release component, comprises an additive gel formed by the gelationof at least two additives selected from the group consisting ofdetergents, dispersants, acids, bases, over based detergents andcombinations thereof; wherein the detergent, when present, comprises asulfonate, a phenate, a salicylate, a carboxylate and mixtures thereof;wherein the dispersant, when present, comprises an N-substituted longchain alkenyl succinimides, polyisobutenyl succinimide, a high molecularweight ester, a Mannich base, an amine dispersant, a polymericdispersant and mixtures thereof; wherein the acid, when present,comprises and acid formed from a polymer containing acidic groups in thebackbone, a polyacidic compound and mixtures thereof.
 4. The compositionof claim 1 wherein (a), the slow release component, comprises a solidthat: (i) has a melting point from 40-250C, (ii) is at least partiallysoluble in the fluid, and (iii) is formed by mixing of one or moreadditives selected from the group consisting of viscosity modifiers,friction modifiers, ashless detergents, cloud point depressants, pourpoint depressants, demulsifiers, flow improvers, anti static agents,ashless dispersants, ashless antioxidants, antifoams, corrosion/rustinhibitors, extreme pressure/antiwear agents, wear reducing agents, sealswell agents, lubricity aids, antimisting agents and mixtures thereof.5. The composition of claim 1 wherein (a), the slow release component,is more than 70 wt % dispersant and detergent.
 6. The composition ofclaim 1 wherein (a), the slow release component, is more than 45 wt %detergent.
 7. The composition of claim 1 wherein (b), the fast releasecomponent, comprises glycerol esters, borated glycerol esters, fattyphosphites, fatty acid amines, fatty epoxides, borated fatty epoxides,alkoxylated fatty amines, borated alkoxylated fatty amines, metal saltsof fatty acids, sulfurized olefins, fatty imidazolines, condensationproducts of carboxylic acids and polyalkylene-polyamines, amine salts ofalkylphosphoric acids, molybdenum-containing friction modifiers, orcombinations thereof.
 8. The composition of claim 1 wherein (a) the slowrelease component, and/or (b) the fast release component, furthercomprises one or more additional additives selected from the groupconsisting of viscosity modifiers, friction modifiers, ashlessdetergents, cloud point depressants, pour point depressants,demulsifiers, flow improvers, anti static agents, ashless dispersants,ashless antioxidants, antifoams, corrosion/rust inhibitors, extremepressure/antiwear agents, wear reducing agents, seal swell agents,lubricity aids, antimisting agents and mixtures thereof.
 9. A process ofreleasing, at controlled rates, one or more additives into a fluid,wherein each additive or group of additives is released at anindependent rate; wherein at least one additive or group of additives isreleased slowly over time into the fluid; and wherein at least oneadditive or group of additives is released quickly into the fluid;wherein the release of the additives into the fluid comprises the stepsof: I. contacting the fluid with a composition comprising: (a) a slowrelease component comprising one or more performance additives in formof a solid or semi-solid mass, wherein the additive components making upthe mass are slowly released into a fluid; and (b) a fast releasecomponent comprising: i. a matrix material which is soluble in thefluid; ii. one or more additives that can be dissolved and/or dispersedinto the matrix material; wherein the additives within the matrixmaterial are quickly released into the fluid; and wherein the weightratio of components (a):(b) is 1:100 to 100:1.
 10. The process of claim9 wherein no more than 80 wt % of (a), the slow release component, isreleased into the fluid over the first 50% or more of the service lifeof the fluid; and wherein at least 80 wt % of (b), the fast releasecomponent, is released into the fluid over the first 25% or less of theservice life of the fluid.
 11. The process of claim 9 wherein (a), theslow release component, and (b), the fast release component, are each inthe form of one or more distinct layers, wherein the one or more layerseach of (a) and (b) are combined to form a controlled release additivepackage, wherein the layers of (a) and (b) may be arranged such thateither component (a) and/or (b) may form one or more external layers,internal layers, or interstitial layers of the controlled releaseadditive package; and wherein one or more of the additive releasepackages are placed in contact with the fluid at one or more locationswithin a fluid system of a device that uses the fluid, resulting in thefast release of one more additives, and the slow release of one or moreadditives, into the fluid.
 12. The process of claim 9 wherein (a), theslow release component, comprises an additive gel formed by the gelationof at least two additives selected from the group consisting ofdetergents, dispersants, acids, bases, over based detergents andcombinations thereof; wherein the detergent, when present, comprises asulfonate, a phenate, a salicylate, a carboxylate and mixtures thereof;wherein the dispersant, when present, comprises an N-substituted longchain alkenyl succinimides, polyisobutenyl succinimide, a high molecularweight ester, a Mannich base, an amine dispersant, a polymericdispersant and mixtures thereof; wherein the acid, when present,comprises and acid formed from a polymer containing acidic groups in thebackbone, a polyacidic compound and mixtures thereof.
 13. The process ofclaim 9 wherein (a), the slow release component, comprises a solid that:(i) has a melting point from 40-250C, (ii) is at least partially solublein the fluid, and (iii) is formed by mixing of one or more additivesselected from the group consisting of viscosity modifiers, frictionmodifiers, ashless detergents, cloud point depressants, pour pointdepressants, demulsifiers, flow improvers, anti static agents, ashlessdispersants, ashless antioxidants, antifoams, corrosion/rust inhibitors,extreme pressure/antiwear agents, wear reducing agents, seal swellagents, lubricity aids, antimisting agents and mixtures thereof.
 14. Anadditive delivery system that comprises a composition comprising: (a) aslow release component comprising one or more performance additives inform of a solid or semi-solid mass, wherein the additive componentsmaking up the mass are slowly released into a fluid; and (b) a fastrelease component comprising: i. a matrix material which is soluble inthe fluid; ii. one or more additives that can be dissolved and/ordispersed into the matrix material; and wherein the additives within thematrix material are quickly released into the fluid; and wherein theweight ratio of components (a):(b) is 1:100 to 100:1; and where theadditive delivery system further comprises a means of contacting thecontrolled release composition with the fluid, resulting in the fastrelease of one more additives, and the slow release of one or moreadditives, into the fluid.
 15. The additive delivery system of claim 14wherein the composition is contained within a fluid filter and whereinone or more additives are released into the fluid as it passes throughthe fluid filter and with a device that utilizes said fluid. 1.